US3249558A - Method for the preparation of vanadium catalysts - Google Patents

Method for the preparation of vanadium catalysts Download PDF

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US3249558A
US3249558A US220906A US22090662A US3249558A US 3249558 A US3249558 A US 3249558A US 220906 A US220906 A US 220906A US 22090662 A US22090662 A US 22090662A US 3249558 A US3249558 A US 3249558A
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vanadium
impregnating
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catalysts
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Kenneth K Kearby
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium

Definitions

  • this invention relates to the use of stable vanadium solutions containing less than the stoichiometric mol ratio of sodium hydroxide which can be used to impregnate supports to form catalyst compositions which compositions are especially effective in the oxidation of carbon monoxide and hydrocarbons found in the exhaust gases from internal combustion engines.
  • stable vanadium solutions containing less than the stoichiometric mol ratio of sodium hydroxide which can be used to impregnate supports to form catalyst compositions which compositions are especially effective in the oxidation of carbon monoxide and hydrocarbons found in the exhaust gases from internal combustion engines.
  • oxidation catalyst is needed and other applications than that referred to specifically will suggest themselves to those skilled in the art.
  • Catalyst should be effective at a relatively low temperature so that it will function soon after the motor has started, i.e., it must have a short warm-up period.
  • Vanadium is not readily available as a soluble decomposable compound, as are the other metal or metal oxide oxidation catalysts. Vanadium is not available as a soluble nitrate, and its ammonium salt is only sparingly soluble. Vanadium catalysts therefore have been previously prepared by tedious multiple impregnations with ammonium meta vanadate or by using expensive complexing agents like oxalic acid. It has now been found that higher concentrations of vanadium can be put in solution by using sodium hydroxide in the mol ratio of (2 to 4)/l (NaOH/V O rather than the stoichiometric ratio of 6/ 1. A solution with a mol ratio of 3/1 is stable for 24 hours or more when using 17.7 g.
  • Sodium hydroxide is a preferred solution reagent because of its low cost, but it will be understood that one may also use other alkali hydroxides, for example potassium hydroxide, is similar mol ratios to those specified for sodium hydroxide.
  • the highly concentrated solutions having a mol ratio 7 of (2 to 4)/ 1 of NaOH/V O may be used to impregnate supports which have previously been impregnated with an acid such as a mineral acid, eg H HCl, HNO or a strong organic acid, e.g. HCOOH, CH COOH.
  • the soluble salts of copper, aluminum andsilver may also be used to preimpregnate the supports.
  • the amount of acid, metal salt or mixture thereof should be at least sufficient to neutralize the sodium ions present in the sodium hydroxide-vanadium oxide subsequently to be added. This will cause either a hydrous oxide of Vanadium or an insoluble vanadate to precipitate onto the support.
  • one may first impregnate with the sodium vanadium oxide solution and then with the acid or precipitating salt solution. The soluble sodium salt may then be removed by washing, and the washed product dried and calcined.
  • compositions prepared on an alumina or silica support'by this method and containing copper and/ or silver, with or without chromium oxide, are especially suitable for catalyzing the oxidation of carbon monoxide and hydrocarbons in automotive exhaust gases.
  • Other supports which may be employed are magnesia, pumice, silicon carbide, graphite, zirconia and alumina silicates.
  • supports prepared from an activated alumina are preferred.
  • Example 2 After draining off 141 cc., the solids were dried at 300 was Washed six times with Water and again dried. The
  • Example 3 The above five samples Were calcined 3 hours at 1000 F. and then tested as catalysts for oxidizing carbon monoxide and isobutane. A fuel containing 2.4% CO, 0.17% iso-C and 3.0% 0 in N was passed at 10,000 v./v./hr. over these catalysts at 1100 F. Conversions were determined, an 0.5 g. pellet of PbBr was dropped on the hot catalyst and conversions again determined. Results are summarized below:
  • vanadium oxide and 'the other metal oxides may be varied. They will usually be in the range of about 2-25% for each oxide.
  • the vanadium oxide, copper oxide and chromium oxide contents are preferably 2.5 to 10%.
  • the added silver oxide is usually 15%.
  • Cr03 When Cr03 is used with V 0 about 5% of each oxide forms a preferred composition, and preferably 5-10% of CuO or Ag O is also included.
  • An improved method for the preparation of vanadium based internal combustion engine exhaust gas oxidation catalysts consisting essentially of impregnating an activated alumina support with a mineral acid, then impregnating with a solution containing sodium hydroxide and vanadium pentoxide having the respective molar ratio of from 2/ 1 to 4/ 1; washing to remove most of the sodium salts; thereafter. impregnating the material with a solution of the saltof a metal oxidation catalyst and finally calcining the resulting composition.
  • metal oxidation catalyst is selected from the class consisting of copper, silver, chromium, cobalt, manganese and their respective oxides.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Description

United States Patent Q 3,249,558 METHOD FOR THE PREPARATION OF VANADIUM CATALYSTS Kenneth K. Kearby, Watchung, N.J., assignor to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Filed Aug. 31, 1962, Ser. No. 220,906 4 Claims. (Cl. 252-464) This invention relates to an improved method for the preparation of vanadium catalysts. Specifically, this invention pertains to the formation of stable vanadium solutions thereby allowing them to be used for impregnating supports with catalytically sufficient amounts of vanadium in a single pass operation. More specifically, this invention relates to the use of stable vanadium solutions containing less than the stoichiometric mol ratio of sodium hydroxide which can be used to impregnate supports to form catalyst compositions which compositions are especially effective in the oxidation of carbon monoxide and hydrocarbons found in the exhaust gases from internal combustion engines. However, they are equally applicable for other purposes where an oxidation catalyst is needed and other applications than that referred to specifically will suggest themselves to those skilled in the art.
The extremely severe conditions which prevail in the catalytic oxidation of carbon monoxide and hydrocarbons contained in the exhaust gases from internal combustion engines set unusually severe criteria for such catalysts which makes the selection of an effective catalyst extremely diflicult. It is generally agreed that an effective catalyst should exhibit the following properties:
(a) Catalyst should be effective at a relatively low temperature so that it will function soon after the motor has started, i.e., it must have a short warm-up period.
(b) It should be highly efiicient in oxidizing exhaust hydrocarbons and carbon monoxide.
(c) It should have a long life, i.e.,
(1) It should not be easily poisoned.
(2) It should withstand at least 1400 F. likely to develop during operation.
(3) It should not be abraded during the continual shaking and occasional shocks characteristic of moving vehicles.
Extensive research in this field has revealed that many catalysts will effectively oxidize the carbon monoxide and hydrocarbons contained in the exhaust gas from internal combustion engines. However, these catalysts have uniformly failed to be economically feasible in automotive afterburners due to their short life. The primary reason for this short life has been the ease with which these catalysts have been poisoned by the metallic compounds contained in the exhaust gases. Especially potent as a poison are the lead compounds formed from the anti-knock additives in the fuel.
It is therefore an object of thepresent invention to provide an improved method for the preparation of vanadium catalyst compositions. It is a further object to provide a method for the preparation of vanadium oxidation catalyst compositions which will be effective in the conversion of carbon monoxide and hydrocarbons found in automotiveexhaust gases to carbon dioxide and water, said catalyst compositions having the property of being relatively resistant to the metallic poisons contained in the exhaust gases. It is a still further object to provide a method for the preparation of stable vanadium solutions so that higher concentrations of the metal can be impregnated on supports by a single operation.
Vanadium is not readily available as a soluble decomposable compound, as are the other metal or metal oxide oxidation catalysts. Vanadium is not available as a soluble nitrate, and its ammonium salt is only sparingly soluble. Vanadium catalysts therefore have been previously prepared by tedious multiple impregnations with ammonium meta vanadate or by using expensive complexing agents like oxalic acid. It has now been found that higher concentrations of vanadium can be put in solution by using sodium hydroxide in the mol ratio of (2 to 4)/l (NaOH/V O rather than the stoichiometric ratio of 6/ 1. A solution with a mol ratio of 3/1 is stable for 24 hours or more when using 17.7 g. V 0 per 50 cc. of water, whereas a ratio of 6/ 1 gives a solution from which Na VO 16H O crystallizes almost immediately. Sodium hydroxide is a preferred solution reagent because of its low cost, but it will be understood that one may also use other alkali hydroxides, for example potassium hydroxide, is similar mol ratios to those specified for sodium hydroxide.
The highly concentrated solutions having a mol ratio 7 of (2 to 4)/ 1 of NaOH/V O may be used to impregnate supports which have previously been impregnated with an acidsuch as a mineral acid, eg H HCl, HNO or a strong organic acid, e.g. HCOOH, CH COOH. The soluble salts of copper, aluminum andsilver may also be used to preimpregnate the supports. The amount of acid, metal salt or mixture thereof should be at least sufficient to neutralize the sodium ions present in the sodium hydroxide-vanadium oxide subsequently to be added. This will cause either a hydrous oxide of Vanadium or an insoluble vanadate to precipitate onto the support. Alternatively one may first impregnate with the sodium vanadium oxide solution and then with the acid or precipitating salt solution. The soluble sodium salt may then be removed by washing, and the washed product dried and calcined.
Compositions prepared on an alumina or silica support'by this method and containing copper and/ or silver, with or without chromium oxide, are especially suitable for catalyzing the oxidation of carbon monoxide and hydrocarbons in automotive exhaust gases. Other supports which may be employed are magnesia, pumice, silicon carbide, graphite, zirconia and alumina silicates. However, supports prepared from an activated alumina are preferred.
The method of the present invention may be further illustrated by the following specific examples.
Example 1 A solution containing g. of CuSO -5H O dissolved in water to a volume of 206 cc. was impregnated onto 216 g. of Alcoa F-l activated alumina and 88 cc. of the solution was then drained off. The drained, copper impregnated alumina was dried at 350 F. It was then cooled and impregnated with 206 cc. of a solution containing 58.5 g. V 0 in NaOH (NaOH/V O mol ratio=3/1). The drained solids after removal of 92 cc. of solution, were dried at 300 F. They were then washed to remove most of the soluble sodium, dried and calcined for 3 hours at 1000 F. The use of a copper or silver salt as the precipitant minimizes the loss of soluble V 0 during washing.
Example 2 After draining off 141 cc., the solids were dried at 300 was Washed six times with Water and again dried. The
gain in weight indicated a V content of about percent. This product was =divided into five parts and impregnated with metal nitrate solutions to add about 10% of the following oxides, one to each part: Cu, Ag, Cr, Co and Mn.
Example 3 The above five samples Were calcined 3 hours at 1000 F. and then tested as catalysts for oxidizing carbon monoxide and isobutane. A fuel containing 2.4% CO, 0.17% iso-C and 3.0% 0 in N was passed at 10,000 v./v./hr. over these catalysts at 1100 F. Conversions were determined, an 0.5 g. pellet of PbBr was dropped on the hot catalyst and conversions again determined. Results are summarized below:
1 Temperature of 1200 F. instead of 1100 F.
The above results show that these catalysts have excellent resistance to poisoning in the presence of relatively large doses of lead. The high activity of the catalyst containing CuO for CO and that of the catalyst containing CrO for isobutane indicates that a combination of these components would be a very effective and stable 'catalyst.
The amounts of vanadium oxide and 'the other metal oxides may be varied. They will usually be in the range of about 2-25% for each oxide. The vanadium oxide, copper oxide and chromium oxide contents are preferably 2.5 to 10%. The added silver oxide is usually 15%. When Cr03 is used with V 0 about 5% of each oxide forms a preferred composition, and preferably 5-10% of CuO or Ag O is also included.
It should be noted that the method of this invention is equally applicable for all purposes where a vanadium oxidation catalyst is needed.- Other applications than those referred to specifically will suggest themselves to those skilled in the art.
What is claimed is:
1. An improved method for the preparation of vanadium based internal combustion engine exhaust gas oxidation catalysts consisting essentially of impregnating an activated alumina support with a mineral acid, then impregnating with a solution containing sodium hydroxide and vanadium pentoxide having the respective molar ratio of from 2/ 1 to 4/ 1; washing to remove most of the sodium salts; thereafter. impregnating the material with a solution of the saltof a metal oxidation catalyst and finally calcining the resulting composition.
2. The method of claim 1 wherein the sodium hydroxide to. vanadium oxide molar ratio is about 3.
3. The method of claim 1 wherein the metal oxidation catalyst is selected from the class consisting of copper, silver, chromium, cobalt, manganese and their respective oxides.
4. The method of claim 3 wherein the metal oxidation catalyst is a copper-chromium mixture.
References Cited by the Examiner UNITED STATES PATENTS 1,851,363 3/1932 Jaeger 252456 XR 1,935,054 11/1933 J aeger 252456 XR 2,081,272 5/1937 Foster 252464 XR 2,206,377 7/1940 Weiss 252464 XR 2,374,932 5/1945 Guyer 252464 XR 2,911,359 11/1959 Hansford 252464 XR 3,000,908 9/1961 Ruthruff 252456 XR 3,025,132 3/1962 Innes 232.2
FOREIGN PATENTS 653,769 12/ 1962 Canada.
BENJAMIN HENKIN, Pit-m Examiner.
MAURICE A. BRINDISI, Examiner.

Claims (1)

1. AN IMPROVED METHOD FOR THE PREPARATION OF VANADIUM BASED INTERNAL COMBUSTION ENGINE EXHAUST GAS OXIDATION CATALYSTS CONSISTING ESSENTIALLY OF IMPREGNATING AN ACTIVATED ALUMINA SUPPORT WITH A MINERAL ACID, THEN IMPREGNATING WITH A SOLUTION CONTAINING SODIUM HYDROXIDE AND VANADIUM PENTOXIDE HAVING THE RESPECTIVE MOLAR RATION OF FROM 2/1 TO 4/1; WASHING TO REMOVE MOST OF THE SODIUM SALTS; THEREAFTER IMPREGNATING THE MATERIAL WITH A SOLUTION OF THE SALT OF A METAL OXIDATION CATALYST AND FINALLY CALCINING THE RESULTING COMPOSITION.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3429656A (en) * 1965-12-10 1969-02-25 Exxon Research Engineering Co Exhaust gas purification
US3447893A (en) * 1966-02-04 1969-06-03 Ethyl Corp Oxidation catalysts
US4010238A (en) * 1973-03-26 1977-03-01 Sumitomo Chemical Company, Limited Proces for selective removal of nitrogen oxides from waste gases
EP0077524A1 (en) * 1981-10-21 1983-04-27 Degussa Aktiengesellschaft Process for lowering the ignition temperature of diesel-oil soot
US4711870A (en) * 1985-04-27 1987-12-08 Bridgestone Corporation Exhaust gas purifying catalyst
US10130935B2 (en) 2015-02-06 2018-11-20 Wisconsin Alumni Research Foundation Enhanced dispersion of two-dimensional metal oxide surface species on silica using an alkali promoter
US10322374B2 (en) 2015-04-21 2019-06-18 Haldor Topsoe A/S Process for the removal of soot from a sulfurous gas stream

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1851363A (en) * 1929-01-30 1932-03-29 Selden Co Catalytic oxidation of organic compounds
US1935054A (en) * 1930-12-02 1933-11-14 Selden Co Catalytic oxidation of organic compounds
US2081272A (en) * 1933-01-06 1937-05-25 Nat Aniline & Chem Co Inc Catalyst and process of making same
US2206377A (en) * 1937-08-06 1940-07-02 Calorider Corp Catalytic oxidation of benzene
US2374932A (en) * 1941-11-15 1945-05-01 Standard Oil Dev Co Dehydrogenation of hydrocarbons
US2911359A (en) * 1956-04-30 1959-11-03 Union Oil Co Desulfurization process and catalyst
US3000908A (en) * 1961-09-19 Catalysis of the vapor phase partial ox-
US3025132A (en) * 1959-08-07 1962-03-13 American Cyanamid Co Method of oxidizing hydrocarbon constituents of exhaust gases
CA653769A (en) * 1962-12-11 Martini Hans Vanadium catalyst

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3000908A (en) * 1961-09-19 Catalysis of the vapor phase partial ox-
CA653769A (en) * 1962-12-11 Martini Hans Vanadium catalyst
US1851363A (en) * 1929-01-30 1932-03-29 Selden Co Catalytic oxidation of organic compounds
US1935054A (en) * 1930-12-02 1933-11-14 Selden Co Catalytic oxidation of organic compounds
US2081272A (en) * 1933-01-06 1937-05-25 Nat Aniline & Chem Co Inc Catalyst and process of making same
US2206377A (en) * 1937-08-06 1940-07-02 Calorider Corp Catalytic oxidation of benzene
US2374932A (en) * 1941-11-15 1945-05-01 Standard Oil Dev Co Dehydrogenation of hydrocarbons
US2911359A (en) * 1956-04-30 1959-11-03 Union Oil Co Desulfurization process and catalyst
US3025132A (en) * 1959-08-07 1962-03-13 American Cyanamid Co Method of oxidizing hydrocarbon constituents of exhaust gases

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3429656A (en) * 1965-12-10 1969-02-25 Exxon Research Engineering Co Exhaust gas purification
US3447893A (en) * 1966-02-04 1969-06-03 Ethyl Corp Oxidation catalysts
US4010238A (en) * 1973-03-26 1977-03-01 Sumitomo Chemical Company, Limited Proces for selective removal of nitrogen oxides from waste gases
EP0077524A1 (en) * 1981-10-21 1983-04-27 Degussa Aktiengesellschaft Process for lowering the ignition temperature of diesel-oil soot
US4711870A (en) * 1985-04-27 1987-12-08 Bridgestone Corporation Exhaust gas purifying catalyst
US10130935B2 (en) 2015-02-06 2018-11-20 Wisconsin Alumni Research Foundation Enhanced dispersion of two-dimensional metal oxide surface species on silica using an alkali promoter
US10322374B2 (en) 2015-04-21 2019-06-18 Haldor Topsoe A/S Process for the removal of soot from a sulfurous gas stream

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